US20160259241A1 - Black photoresist composition, method of preparing the same, color filter, and display device - Google Patents

Black photoresist composition, method of preparing the same, color filter, and display device Download PDF

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Publication number
US20160259241A1
US20160259241A1 US14/387,770 US201314387770A US2016259241A1 US 20160259241 A1 US20160259241 A1 US 20160259241A1 US 201314387770 A US201314387770 A US 201314387770A US 2016259241 A1 US2016259241 A1 US 2016259241A1
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infrared light
emitting
photoresist composition
black photoresist
composition capable
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US9529256B2 (en
Inventor
Jiuxia YANG
Feng Bai
Yiming Zhao
Xiao Sun
Bing Bai
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BOE Technology Group Co Ltd
Beijing BOE Optoelectronics Technology Co Ltd
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BOE Technology Group Co Ltd
Beijing BOE Optoelectronics Technology Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix

Definitions

  • Embodiments of the present invention relates to a black photoresist composition capable of emitting infrared light, a method of preparing the black photoresist composition capable of emitting infrared light, a color filter comprising a Black Matrix formed from the black photoresist composition capable of emitting infrared light, and a display device comprising the color filter.
  • Conventional display devices achieve color display by means of conventional color filters.
  • Conventional color filters utilize a black photoresist material comprising components like colorants for providing a color, ethenoid unsaturated monomers, alkali-soluble resins, solvents, photoinitiators, and the like.
  • far-infrared light exhibits relative strong penetrability and radiation, has remarkable temperature-controlling effect and resonant effect.
  • far-infrared light can be resonated with in vivo water molecules to activate the water molecules and improve the inter-molecular binding force, thereby activating biological macromolecules like proteins, etc, and allowing cells in organisms to be at the highest vibrational levels.
  • far-infrared heat energy can be transferred to a deeper subcutaneous site so that the temperature of deep zone increases and the produced warm diffuses from the inside out.
  • Such effect expands capillary vessels, facilitates blood circulation, enhances metabolism among various tissues, increases regeneration capacity of tissues, improves immunity of bodies, and adjusts abnormally excited mental state, thereby producing therapeutic and health caring effect.
  • a black photoresist composition further having an function of emitting infrared light is developed on the basis of conventional black photoresist materials so that the display device produced therefrom can have both conventional display effect and therapeutic and health caring effect.
  • An embodiment of the present invention provides a black photoresist composition capable of emitting infrared light, which can not only emit a sufficient amount of infrared light, but also maintain conventional display properties, such as, optical density, chromaticity, etc., thereby achieving both health caring and display.
  • the black photoresist composition capable of emitting infrared light comprises, based on the total weight of the composition, 2% to 15% of a color mixed material, 30% to 90% of a solvent, 2% to 20% of an alkali-soluble resin, 2% to 20% of an ethenoid unsaturated monomer, 0.01% to 1% of a photoinitiator, and 0.005% to 0.02% of other additives; wherein, the color mixed material comprises a colorant and a surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1.
  • the color mixed material comprises the colorant and the surface-modified infrared light-emitting material at a weight ratio of 6:1 to 1:1.
  • the infrared light-emitting material is one or more selected from the group consisting of tourmaline, biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide.
  • the infrared light-emitting material is subject to surface modification with a polymeric material.
  • the polymeric material is a methyl methacrylate-co-styrene-co-maleimide copolymer.
  • the surface-modified infrared light-emitting material has a mean particle diameter of 1 nm to 200 nm.
  • the tourmaline is black tourmaline having a density of 3.06 to 3.26 g/cm 3 and a refraction index of 1.62 to 1.64.
  • Another embodiment of the present invention provides a color filter comprising a Black Matrix formed from the aforesaid black photoresist composition capable of emitting infrared light.
  • Another embodiment of the present invention provides a display device comprising the aforesaid color filter.
  • the display device made from the black photoresist composition capable of emitting infrared light can not only emit a sufficient amount of infrared light, but also maintain original display properties like optical density (OD) value, etc., thereby achieving both health caring and display.
  • OD optical density
  • An embodiment of the present invention provides a black photoresist composition capable of emitting infrared light, comprises, based on the total weight of the composition, 2% to 15% of a color mixed material, 30% to 90% of a solvent, 2% to 20% of an alkali-soluble resin, 2% to 20% of an ethenoid unsaturated monomer, 0.01% to 1% of a photoinitiator, and 0.005% to 0.02% of other additives.
  • the color mixed material comprises 2 to 15% of the total weight of the composition, preferably, 5% to 15%, more preferably 5% to 10%.
  • the aforesaid color mixed material comprises the colorant and the surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1, preferably 11:3 to 1:1, more preferably 9:5 to 1:1.
  • the aforesaid colorant can be black pigments, black dyes, or a mixture of two or more thereof.
  • the examples of the aforesaid black pigments can comprise carbon black pigments and organic black pigments.
  • Carbon black pigments can be, e.g., Printex L6, Printex L. Printex55, Printex 45, Printex 60, Super Black 550, Super Black 350, Printex 35, Super Black 250, Printex 25, Super Black 100, Printex 200, Hiblack 30, Hiblack 30L available from DEGUSSA; Raven 1255, Raven 1200, Raven 1170, Raven 1100 Ultra, Raven 1060 Ultra, Raven 1040, Raven 1035, Raven 1020, Raven 1000, Raven 890, Raven 860 Ultra, Raven 850, Raven 820, Raven 760 Ultra, Raven 460, Raven 450, Raven 410, Raven H2O, Raven 825 OB, Raven 680 OB available from Columbia; and R99R, R250R, R330R, R400R, R660R, ML, DL430 available from CABOT; and the like.
  • Organic black pigments can be e.g., L0080 and L0086 available from BASF; and CCA1 and CCA2 available from Nippon Central Synthetic Chemical Co., Ltd.
  • the examples of the aforesaid black dyes can comprise C.I. Direct Black19, C.I. Direct Black22, C.I. Direct Black154, C.I. Direct Black168, dyes11, dyes12, dyes13, dyes14, dyes15, dyes16, dyes17, dyes18, and the like.
  • the aforesaid infrared light-emitting material is a material which can produce infrared light through heat exchange, and the examples thereof can comprise one or more selected from the group consisting from the group consisting of tourmaline ([Na,K,Ca][Mg,F,Mn,Li,Al]3[Al,Cr,Fe,V]6[BO3]3[Si6O18][OH,F]4), biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide.
  • tourmaline [Na,K,Ca][Mg,F,Mn,Li,Al]3[Al,Cr,Fe,V]6[BO3]3[Si6O18][OH,F]4
  • biological carbon far-infrared ceramics
  • bowlder powders alumina, copper oxide, silver oxide and silicon carbide.
  • the infrared light-emitting material can have a mean particle diameter of 1 nm to 200 nm, preferably 5 nm to 150 nm, more preferably 10 nm to 100 nm, and most preferably 25 nm to 75 nm.
  • the infrared light-emitting material is preferably tourmaline, biological carbon, alumina or silicon carbide.
  • the tourmaline is preferably black tourmaline having a hardness of 7 to 7.2, a density of 3.06 to 3.26 g/cm 3 , and a refraction index of 1.62 to 1.64.
  • the biological carbon has preferably a specific area of 550 to 750 m 2 /g and a density of 1.3 to 1.5 g/cm 3 .
  • the aforesaid infrared light-emitting material without surface modification cannot be used in the embodiments of the present invention because the incompatibility of such unmodified material with the organic resin component and the pigment component in the black photoresist composition system is likely to cause the precipitation and phase separation of the photoresist composition, thereby resulting in the deterioration of properties of the photoresist material and affecting the uniformity of display effect.
  • the aforesaid infrared light-emitting material Prior to use, is subject to surface modification to modify its surface morphometry and grain boundary structure, thereby changing the activity of material, increasing its heat exchange capacity, and enabling it to emit far-infrared light having a specific wavelength at a high specific radiance.
  • the surface modification of the infrared light-emitting material can comprise:
  • the solvent used in the aforesaid steps c can be one or more of fatty alcohol, ethylene glycol ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, monomethyl ether ethylene glycol ester, ⁇ -butyraolactone, ethyl 3-ethoxypropriate, butylcarbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, xylene, and isopropanol.
  • the dispersant used in the above steps can be conventional dispersing agents, e.g., BYK 410, BYK 110, BYK 163, BYK 161, BYK 2000, CN2284, Solsperse32500, Solsperse22000, and the like.
  • the dispersant can comprise 5-15 wt % of the nano-dispersion, preferably 7 to 12%.
  • the solvent can comprises 30-90 wt % of the total weight of the composition, preferably 40-90 wt %, and more preferably 45-90 wt %.
  • the solvent can be one or more selected from the group consisting of acidic solvents, basic solvents, and neutral solvents.
  • acidic solvents can comprise formic acid, acetic acid, chloroform, or the like.
  • basic solvents can comprise some basic ketones, esters, ethers, or certain aromatic hydrocarbons, etc.
  • neutral solvents can comprise fatty alcohol, ethylene glycol ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, monomethyl ether ethylene glycol ester, ⁇ -butyraolactone, ethyl 3-ethoxypropriate, butylcarbitol, butylcarbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, xylene, isopropanol, and the like.
  • the solvent can be propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, butylcarbitol, butylcarbitol acetate or ⁇ -butyraolactone, or their mixture.
  • the alkali-soluble resin can comprise 2 wt % to 20 wt % based on the total weight of the composition, preferably 5 wt % to 20 wt %, and more preferably 5 wt % to 15 wt %.
  • the alkali-soluble resin can be aromatic acid (meth)acrylic acid semi-ester (e.g., SB401, SB404 available from Sartomer Co., Ltd.), a copolymer of styrene and maleic anhydride, or any combination thereof.
  • the monomer can be ethenoid unsaturated monomer, and comprise 2 wt % to 20 wt % of the total weight of the composition, preferably 5 wt % to 20 wt %, and more preferably 5 wt % to 15 wt %.
  • the ethenoid unsaturated monomer can be ethenoid chloride, styrene, methyl methacrylate, maleimide, butadiene, methyl acrylate, epoxy acrylate, bisphenol A-type methyl epoxy acrylate, multi-functional (meth)acrylate monomers (e.g., ethoxylated trimethoxypropane triacrylate, pentaerythritol, etc.), or any combination thereof.
  • the photoinitiator can comprise 0.01 wt % to 1 wt % of the total weight of the composition, wherein the photoinitiator can be a-aminoketone-based photoinitiators, such as, Irgacure 907, Igracure 369, Irgacure 1300; or acylphosphine oxide photoinitiator, such as, Irgacure 819, Irgacure 819DW, Irgacure 2010, Darocur TPO, Darocur 4265; a-hydroxyketone-based photoinitiator, such as, Darocur 1173, Irgacure 184, Irgacure 2959, Irgacure 500, Irgacure 1000; or phenylglyoxylic acid-based photoinitiator, such as, Darocur MBF, Irgacur
  • the other additives can comprise 0.005 wt % to 0.02 wt % of the total weight of the composition, preferably 0.005 wt % to 0.015 wt %, and more preferably 0.005 wt % to 0.01 wt %, wherein the additives can be adhesion promoters, leveling agents, defoaming agents, photo-stabilizers, and the like.
  • a colorant is mixed with the surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1 to give the color mixed material.
  • the aforesaid color mixed material, solvent, alkali-soluble resin, ethenoid unsaturated monomer, photoinitiator, and other additives are homogenously with the aforesaid amounts by means of, e.g., stirring, shaking, or the like, thereby preparing the black photoresist composition capable of emitting infrared light of the embodiments of the present invention.
  • the black photoresist composition comprising the aforesaid components can not only maintain conventional display properties like chromaticity, transmissivity, etc., but also emit far-infrared light with a wavelength ranging from 5 to 15 microns and a specific radiance ranging from 0.35 to 0.95 so as to provide a health caring effect.
  • a dispersant BYK 161
  • PMA propylene glycol monomethyl ether acetate
  • Azobisisovaleronitrile was dissolved into PMA to produce a saturatued solution of azobisisovaleronitrile in PMA, and the weight percent upon complete dissolution was recorded. Nitrogen was purged into the aforesaid four-neck flask at 35° C. The saturated solution of azobisisovaleronitrile in PMA as produced above was added with stirring in an amount to allow the net concent of the azobisisovaleronitrile as initiator to be 1% of the total net content of the aforesaid monomer, and the reaction was kept for 30 min. After completion of reaction, 100 mL PMA at 5° C. was added with stirring to cool the reaction products to room temperature.
  • reaction products were filtered.
  • the filtered solids were washed with 50 ml PMA three times, and dried at 90° C. for 15min, thereby obtaining alumina particles modified with methyl methacrylate-co-styrene-co-maleimide copolymer and having having a mean particle diameter of 24 nm.
  • Black pigment RAVEN 760 ULTRA was mixed with the aforesaid modified alumina particles at a weight ratio of 19:1 to produce a color mixed material-1.
  • Color mixed material-2 to color mixed material-10 were prepared in accordance with the same method as Example 1, except that the mixing ratio of the black pigment to the modified infrared light-emitting material were shown in Table 1.
  • the alkali-soluble resins D-1 (10%) and D-2 (2%), the ethenoid unsaturated monomers E-1 (10%) and E-2 (3.8%), the photoinitiators F-1 (0.007%) and F-2 (0.008%), as well as the other additives G-1 (0.002%) and G-2 (0.013%) were added into a mixed solvent comprising the solvent C-2 (30%) and C-3 (10%), and stirred until these components were thoroughly dissolved to produce a photo-curable solution.
  • the color mixed material dispersion-1 as produced above was added in to the photo-curable solution, and ground with a sand mill. During grinding, the solvent C-1 was supplemented so that the black photoresist composition comprised 15 wt % of the color mixed material and 19.17 wt % of the solvent C-1, thereby producing the black photoresist composition-1.
  • the black photoresist composition-2 to the black photoresist composition-12 were prepared by the same methods as EXAMPLES 2 and 3, respectively, except that the ratio of various components were shown in Table 1.
  • the black photoresist composition-1 to the black photoresist composition-10 of Examples 3 to 12 were applied onto glass substrate by means of spin coating.
  • the substrates coated with the black photoresist composition were baked at a temperature of 90° C., and then subject to UV radiation with an illuminance of 180 mJ/cm 2 for 15 seconds for exposing the aforesaid black photoresist composition.
  • the exposed glass substrates were developed in a basic developer, and then baked at a temperature of 200° C. for 20 min, to form black rectangular patterns 1 to 10, which had a thickness of 1.5 ⁇ m.
  • the specific radiance of infrared light of the photoresist composition is also low. Over the increasing of the content of the infrared light-emitting material in the color mixed material, the specific radiance of infrared light of the photoresist composition increases, but does not yet result in remarkable effect on the optical density of the photoresist material.
  • a dispersant BYK 161
  • PMA propylene glycol monomethyl ether acetate
  • the resultant mixture was stirred to be homogeneous, and ground in a sand mill to the extent that the mean particle diameter of alumina is 17 nm, thereby produce an alumina nano-dispersion.
  • the alumina nano-dispersion was subject to removal of solvent, thereby producing alumina nanoparticles.
  • the black pigment RAVEN 760 ULTRA was mixed with the aforesaid alumina nanoparticles at a weight ratio of 19:1 to produce a color mixed material.
  • the comparative black photoresist composition was prepared in accordance with the method of Example 3.
  • Example 3 The two black photoresist compositions of Example 3 and Comparative Example 1 were placed under shade environment at 0 to 4° C., and then observed for the delamination and precipitation of the photoresist composition.
  • the comparative black photoresist composition after 24 hours, there were crusting on the surface and some precipitates at the bottom of the containment; and after 48 hours, there appeared a large amount of agglomerates with stirring, and solid particles agglomerated seriously.
  • the black photoresist composition-1 Until 48 hours, there appeared no crusting on the surface or precipitate at the bottom; while stirring did not result in caking or agglomeration.
  • the black photoresist composition capable of emitting infrared light of the embodiments of the present invention can emit far-infrared light having a health caring effect while maintaining conventional display properties due to the incorporation of surface-modified infrared light-emitting material nanoparticles.

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Abstract

A black photoresist composition capable of emitting infrared light, a method of preparing the black photoresist composition capable of emitting infrared light, a color filter comprising a Black Matrix formed from the black photoresist composition capable of emitting infrared light, and a display device including the color filter. The black photoresist composition capable of emitting infrared light includes, based on the total weight of the composition, 2% to 15% of a color mixed material, 30% to 90% of a solvent, 2% to 20% of an alkali-soluble resin, 2% to 20% of an ethenoid unsaturated monomer, 0.01% to 1% of photoinitiator, and 0.005% to 0.02% of other additives; wherein the color mixed material includes a colorant and a surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1.

Description

    TECHNICAL FIELD
  • Embodiments of the present invention relates to a black photoresist composition capable of emitting infrared light, a method of preparing the black photoresist composition capable of emitting infrared light, a color filter comprising a Black Matrix formed from the black photoresist composition capable of emitting infrared light, and a display device comprising the color filter.
    • BACKGROUND
  • Over the rapid development of display techniques, customers require a display device to not only have a clear and emulational display effect, but also to exhibit multi-functionality, such as, recreational and healthy functions.
  • Conventional display devices achieve color display by means of conventional color filters. Conventional color filters utilize a black photoresist material comprising components like colorants for providing a color, ethenoid unsaturated monomers, alkali-soluble resins, solvents, photoinitiators, and the like.
  • It is well known that far-infrared light exhibits relative strong penetrability and radiation, has remarkable temperature-controlling effect and resonant effect. After absorption by human bodies, far-infrared light can be resonated with in vivo water molecules to activate the water molecules and improve the inter-molecular binding force, thereby activating biological macromolecules like proteins, etc, and allowing cells in organisms to be at the highest vibrational levels. Due to the resonant effect of biological cells, far-infrared heat energy can be transferred to a deeper subcutaneous site so that the temperature of deep zone increases and the produced warm diffuses from the inside out. Such effect expands capillary vessels, facilitates blood circulation, enhances metabolism among various tissues, increases regeneration capacity of tissues, improves immunity of bodies, and adjusts abnormally excited mental state, thereby producing therapeutic and health caring effect.
  • Based on the above described requirements and technical background, a black photoresist composition further having an function of emitting infrared light is developed on the basis of conventional black photoresist materials so that the display device produced therefrom can have both conventional display effect and therapeutic and health caring effect.
    • SUMMARY
  • An embodiment of the present invention provides a black photoresist composition capable of emitting infrared light, which can not only emit a sufficient amount of infrared light, but also maintain conventional display properties, such as, optical density, chromaticity, etc., thereby achieving both health caring and display.
  • In an embodiment of the present invention, the black photoresist composition capable of emitting infrared light comprises, based on the total weight of the composition, 2% to 15% of a color mixed material, 30% to 90% of a solvent, 2% to 20% of an alkali-soluble resin, 2% to 20% of an ethenoid unsaturated monomer, 0.01% to 1% of a photoinitiator, and 0.005% to 0.02% of other additives; wherein, the color mixed material comprises a colorant and a surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1.
  • In an aspect of the present invention, the color mixed material comprises the colorant and the surface-modified infrared light-emitting material at a weight ratio of 6:1 to 1:1.
  • In another aspect of the present invention, the infrared light-emitting material is one or more selected from the group consisting of tourmaline, biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide.
  • In another aspect of the present invention, the infrared light-emitting material is subject to surface modification with a polymeric material.
  • The polymeric material is a methyl methacrylate-co-styrene-co-maleimide copolymer.
  • The surface-modified infrared light-emitting material has a mean particle diameter of 1 nm to 200 nm.
  • In another aspect of the present invention, the tourmaline is black tourmaline having a density of 3.06 to 3.26 g/cm3 and a refraction index of 1.62 to 1.64.
  • Another embodiment of the present invention provides a method of preparing a black photoresist composition capable of emitting infrared light comprising:
      • grinding and dispersing an infrared light-emitting material into a solvent to give a nano-dispersion comprising infrared light-emitting material nanoparticles having a mean particle diameter of 1 nm to 200 nm;
      • surface-modifying the infrared light-emitting material nanoparticles in the nano-dispersion with a polymeric material, followed by removing the solvent, to give polymeric material-modified infrared light-emitting material nanoparticles;
      • mixing the polymeric material-modified infrared light-emitting material nanoparticles with a colorant to give a color mixed material, and
      • mixing the color mixed material with a solvent, an alkali-soluble resin, an ethenoid unsaturated monomer, a photoinitiator, and other additives to give the black photoresist composition capable of emitting infrared light.
  • Another embodiment of the present invention provides a color filter comprising a Black Matrix formed from the aforesaid black photoresist composition capable of emitting infrared light.
  • Another embodiment of the present invention provides a display device comprising the aforesaid color filter.
  • The display device made from the black photoresist composition capable of emitting infrared light can not only emit a sufficient amount of infrared light, but also maintain original display properties like optical density (OD) value, etc., thereby achieving both health caring and display.
    • DETAILED DESCRIPTION
  • An embodiment of the present invention provides a black photoresist composition capable of emitting infrared light, comprises, based on the total weight of the composition, 2% to 15% of a color mixed material, 30% to 90% of a solvent, 2% to 20% of an alkali-soluble resin, 2% to 20% of an ethenoid unsaturated monomer, 0.01% to 1% of a photoinitiator, and 0.005% to 0.02% of other additives.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the color mixed material comprises 2 to 15% of the total weight of the composition, preferably, 5% to 15%, more preferably 5% to 10%.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the aforesaid color mixed material comprises the colorant and the surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1, preferably 11:3 to 1:1, more preferably 9:5 to 1:1.
  • The aforesaid colorant can be black pigments, black dyes, or a mixture of two or more thereof.
  • The examples of the aforesaid black pigments can comprise carbon black pigments and organic black pigments. Carbon black pigments can be, e.g., Printex L6, Printex L. Printex55, Printex 45, Printex 60, Super Black 550, Super Black 350, Printex 35, Super Black 250, Printex 25, Super Black 100, Printex 200, Hiblack 30, Hiblack 30L available from DEGUSSA; Raven 1255, Raven 1200, Raven 1170, Raven 1100 Ultra, Raven 1060 Ultra, Raven 1040, Raven 1035, Raven 1020, Raven 1000, Raven 890, Raven 860 Ultra, Raven 850, Raven 820, Raven 760 Ultra, Raven 460, Raven 450, Raven 410, Raven H2O, Raven 825 OB, Raven 680 OB available from Columbia; and R99R, R250R, R330R, R400R, R660R, ML, DL430 available from CABOT; and the like.
  • Organic black pigments can be e.g., L0080 and L0086 available from BASF; and CCA1 and CCA2 available from Nippon Central Synthetic Chemical Co., Ltd.
  • The examples of the aforesaid black dyes can comprise C.I. Direct Black19, C.I. Direct Black22, C.I. Direct Black154, C.I. Direct Black168, dyes11, dyes12, dyes13, dyes14, dyes15, dyes16, dyes17, dyes18, and the like.
  • The aforesaid infrared light-emitting material is a material which can produce infrared light through heat exchange, and the examples thereof can comprise one or more selected from the group consisting from the group consisting of tourmaline ([Na,K,Ca][Mg,F,Mn,Li,Al]3[Al,Cr,Fe,V]6[BO3]3[Si6O18][OH,F]4), biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide. The infrared light-emitting material can have a mean particle diameter of 1 nm to 200 nm, preferably 5 nm to 150 nm, more preferably 10 nm to 100 nm, and most preferably 25 nm to 75 nm.
  • The infrared light-emitting material is preferably tourmaline, biological carbon, alumina or silicon carbide. Of those, the tourmaline is preferably black tourmaline having a hardness of 7 to 7.2, a density of 3.06 to 3.26 g/cm3, and a refraction index of 1.62 to 1.64. The biological carbon has preferably a specific area of 550 to 750 m2/g and a density of 1.3 to 1.5 g/cm3.
  • The aforesaid infrared light-emitting material without surface modification cannot be used in the embodiments of the present invention because the incompatibility of such unmodified material with the organic resin component and the pigment component in the black photoresist composition system is likely to cause the precipitation and phase separation of the photoresist composition, thereby resulting in the deterioration of properties of the photoresist material and affecting the uniformity of display effect. Prior to use, the aforesaid infrared light-emitting material is subject to surface modification to modify its surface morphometry and grain boundary structure, thereby changing the activity of material, increasing its heat exchange capacity, and enabling it to emit far-infrared light having a specific wavelength at a high specific radiance.
  • The surface modification of the infrared light-emitting material can comprise:
      • 1) Grinding and dispersing the infrared light-emitting material into a solvent to give a nano-dispersion comprising the infrared light-emitting material nanoparticles having a mean particle diameter of 1 nm to 200 nm. The primary object of this step is to nano-crystallize the infrared light-emitting material to give infrared light-emitting material nanoparticles. The grinding and dispersing can be achieved with conventional methods for preparing nano materials, e.g., they can be achieved with conventional grinding equipments (such as, ball grinder, sand mill, etc.) and dispersants in an organic solvent. Based on the total weight of the nano-dispersion, the infrared light-emitting material can comprise 10 to 15 wt % of the nano-dispersion.
      • 2) Subjecting the nano-crystallized infrared light-emitting material to a further surface modification. The primary object of this step is to modify the surface characteristics of the dispersed nanoparticles in step 1) so that these modified nanoparticles can be compatible with the black photoresist composition system. The step comprises, in particular:
        • dissolving azo initiators (such as, azobisisovaleronitrile, azobisisobutyronitrile, azobisisocapronitrile, azobisisoheptanenitrile, etc.) in an organic solvent for use in next step;
        • charging the nano-dispersion of the infrared light-emitting material into a four-neck flask, while stirring, vibrating (at a frequency of more than 50 Hz) or shaking the nano-dispersion;
        • adding an solution of monomers methyl methacrylate, styrene, and maleimide (1:1-2:1-2/mol) in an organic solvent (monomer:solvent=1:1-3/vol) into the aforesaid four-neck flask, wherein the infrared light-emitting material comprises 8-25% of the mixed solution in the four-neck flask, preferably 10 to 20%, and more preferably 12 to 17%;
        • adding an solution of azo initiators into the aforesaid four-neck flask in an amount of 1-5% based on the total weight of monomers at a temperature of 35° C. to 60 ° C. and under nitrogen protective atmosphere, and reacting the mixture under stirring, vibrating, or shaking for 30 min to 90 min;
        • after completion of reaction, adding an organic solvent at 5 to 10° C. for cooling, while stirring the reaction mixture until the reaction product cools to room temperature;
        • after filtration, washing the filtered solids with the aforesaid organic solvent three times, and drying the solids at 70 to 100° C. for 5 to 20 min, to give the surface-modified infrared light-emitting material.
  • The solvent used in the aforesaid steps c can be one or more of fatty alcohol, ethylene glycol ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, monomethyl ether ethylene glycol ester, γ-butyraolactone, ethyl 3-ethoxypropriate, butylcarbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, xylene, and isopropanol.
  • The dispersant used in the above steps can be conventional dispersing agents, e.g., BYK 410, BYK 110, BYK 163, BYK 161, BYK 2000, CN2284, Solsperse32500, Solsperse22000, and the like. The dispersant can comprise 5-15 wt % of the nano-dispersion, preferably 7 to 12%.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the solvent can comprises 30-90 wt % of the total weight of the composition, preferably 40-90 wt %, and more preferably 45-90 wt %. The solvent can be one or more selected from the group consisting of acidic solvents, basic solvents, and neutral solvents. The examples of acidic solvents can comprise formic acid, acetic acid, chloroform, or the like. The examples of basic solvents can comprise some basic ketones, esters, ethers, or certain aromatic hydrocarbons, etc. The examples of neutral solvents can comprise fatty alcohol, ethylene glycol ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, monomethyl ether ethylene glycol ester, γ-butyraolactone, ethyl 3-ethoxypropriate, butylcarbitol, butylcarbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, xylene, isopropanol, and the like. Preferably, the solvent can be propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, butylcarbitol, butylcarbitol acetate or γ-butyraolactone, or their mixture.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the alkali-soluble resin can comprise 2 wt % to 20 wt % based on the total weight of the composition, preferably 5 wt % to 20 wt %, and more preferably 5 wt % to 15 wt %. The alkali-soluble resin can be aromatic acid (meth)acrylic acid semi-ester (e.g., SB401, SB404 available from Sartomer Co., Ltd.), a copolymer of styrene and maleic anhydride, or any combination thereof.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the monomer can be ethenoid unsaturated monomer, and comprise 2 wt % to 20 wt % of the total weight of the composition, preferably 5 wt % to 20 wt %, and more preferably 5 wt % to 15 wt %. The ethenoid unsaturated monomer can be ethenoid chloride, styrene, methyl methacrylate, maleimide, butadiene, methyl acrylate, epoxy acrylate, bisphenol A-type methyl epoxy acrylate, multi-functional (meth)acrylate monomers (e.g., ethoxylated trimethoxypropane triacrylate, pentaerythritol, etc.), or any combination thereof.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the photoinitiator can comprise 0.01 wt % to 1 wt % of the total weight of the composition, wherein the photoinitiator can be a-aminoketone-based photoinitiators, such as, Irgacure 907, Igracure 369, Irgacure 1300; or acylphosphine oxide photoinitiator, such as, Irgacure 819, Irgacure 819DW, Irgacure 2010, Darocur TPO, Darocur 4265; a-hydroxyketone-based photoinitiator, such as, Darocur 1173, Irgacure 184, Irgacure 2959, Irgacure 500, Irgacure 1000; or phenylglyoxylic acid-based photoinitiator, such as, Darocur MBF, Irgacure 754; oxyacyloxime ester-based photoinitiator, such as, OXE-01, OXE-02, Quanta cure PDO; or any mixture thereof.
  • In the black photoresist composition capable of emitting infrared light of the embodiments of the present invention, the other additives can comprise 0.005 wt % to 0.02 wt % of the total weight of the composition, preferably 0.005 wt % to 0.015 wt %, and more preferably 0.005 wt % to 0.01 wt %, wherein the additives can be adhesion promoters, leveling agents, defoaming agents, photo-stabilizers, and the like.
  • A colorant is mixed with the surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1 to give the color mixed material.
  • The aforesaid color mixed material, solvent, alkali-soluble resin, ethenoid unsaturated monomer, photoinitiator, and other additives are homogenously with the aforesaid amounts by means of, e.g., stirring, shaking, or the like, thereby preparing the black photoresist composition capable of emitting infrared light of the embodiments of the present invention. Thus, the black photoresist composition comprising the aforesaid components can not only maintain conventional display properties like chromaticity, transmissivity, etc., but also emit far-infrared light with a wavelength ranging from 5 to 15 microns and a specific radiance ranging from 0.35 to 0.95 so as to provide a health caring effect.
    • EXAMPLES
  • The raw materials used in each examples are listed as follows:
      • A, Colorant: Raven 760 Ultra
      • B, Infrared Light-emitting Material:
      • B-1: black tourmaline: density: 3.06 g/cm3, refraction index: 1.62, hardness: 7
      • B-2: biological carbon: specific area: 600 m2/g, density: 1.3 g/cm3
      • B-3: alumina: purity: more than 99.9%
      • C, Solvent
      • C-1: propylene glycol monomethyl ether acetate (PMA)
      • C-2: ethyl 3-ethoxypropriate(EEP)
      • C-3: n-butanol (n-BuOH)
      • D, Alkali-Soluble Resin
      • D-1: SB 401 (Sartomer)
      • D-2: SB 404 (Sartomer)
      • E, Ethenoid Unsaturated monomer
      • E-1: EBE 350 (Cytex)
      • E-2: dipentaerythritol penta/hexaacrylate (DPHA) (Cytex)
      • F, Inflator
      • F-1: Irgacure 369 (Ciba Special Chemicals)
      • F-2: OXE-02(Ciba Special Chemicals)
      • G, Other Additives
      • G-1: adhesion promoter A-186
      • G-2: leveling agent BYK 333
      • H, Dispersant
      • H-1: BYK 161
      • H-2: Solsperse 32500
      • H-3: CN 2284
      • H-4: Solsperse 22000
    Preparation of Color Mixed Material Example 1
  • 5 g of a dispersant, BYK 161, were added into 95 g of a solvent, propylene glycol monomethyl ether acetate (PMA), and then 11.1 g of alumina particles were added. The resultant mixture was stirred to be homogeneous, and ground to allow the formed nanoparticles of alumina to have a mean diameter of 17 nm, thereby producing an alumina nano-dispersion.
  • Monomers, methyl methacrylate, styrene, and maleimide (1:1:1/mol), were dissolved in a solvent PMA (monomer: solvent=1:1/vol). and then 27.7 g of the resultant solution was charged into a four-neck flask equipped with stirrer, thermometer, purge tube, and drop funnel so that the alumina comprised 8% of the weight of the mixed solution.
  • Azobisisovaleronitrile was dissolved into PMA to produce a saturatued solution of azobisisovaleronitrile in PMA, and the weight percent upon complete dissolution was recorded. Nitrogen was purged into the aforesaid four-neck flask at 35° C. The saturated solution of azobisisovaleronitrile in PMA as produced above was added with stirring in an amount to allow the net concent of the azobisisovaleronitrile as initiator to be 1% of the total net content of the aforesaid monomer, and the reaction was kept for 30 min. After completion of reaction, 100 mL PMA at 5° C. was added with stirring to cool the reaction products to room temperature.
  • The aforesaid reaction products were filtered. The filtered solids were washed with 50 ml PMA three times, and dried at 90° C. for 15min, thereby obtaining alumina particles modified with methyl methacrylate-co-styrene-co-maleimide copolymer and having having a mean particle diameter of 24 nm.
  • Black pigment RAVEN 760 ULTRA was mixed with the aforesaid modified alumina particles at a weight ratio of 19:1 to produce a color mixed material-1.
    • Example 2
  • Color mixed material-2 to color mixed material-10 were prepared in accordance with the same method as Example 1, except that the mixing ratio of the black pigment to the modified infrared light-emitting material were shown in Table 1.
    • Preparation of Black Photoresist Composition Example 3
  • 8 g of Solsperse 22000, 75 g of Solsperse 32500, 40 g of CN 2284 and 423.5 g of the solvent PMA were mixed homogeneously by means of stirring to produce a dispersant solution. To this solution, 100 g of the color mixed material-1 prepared in Example 1 was added, and the mixture was stirred to moisten sufficiently the pigment to produce a mixed solution. The mixed solution was ground and dispersed with a sand mill to produce a color mixed material dispersion-1, which comprised 15.5 wt % of the color mixed material-1.
  • The alkali-soluble resins D-1 (10%) and D-2 (2%), the ethenoid unsaturated monomers E-1 (10%) and E-2 (3.8%), the photoinitiators F-1 (0.007%) and F-2 (0.008%), as well as the other additives G-1 (0.002%) and G-2 (0.013%) were added into a mixed solvent comprising the solvent C-2 (30%) and C-3 (10%), and stirred until these components were thoroughly dissolved to produce a photo-curable solution. The color mixed material dispersion-1 as produced above was added in to the photo-curable solution, and ground with a sand mill. During grinding, the solvent C-1 was supplemented so that the black photoresist composition comprised 15 wt % of the color mixed material and 19.17 wt % of the solvent C-1, thereby producing the black photoresist composition-1.
    • Examples 4 to 12
  • The black photoresist composition-2 to the black photoresist composition-12 were prepared by the same methods as EXAMPLES 2 and 3, respectively, except that the ratio of various components were shown in Table 1.
    • Application of the Black Photoresist Composition
  • The black photoresist composition-1 to the black photoresist composition-10 of Examples 3 to 12 were applied onto glass substrate by means of spin coating. The substrates coated with the black photoresist composition were baked at a temperature of 90° C., and then subject to UV radiation with an illuminance of 180 mJ/cm2 for 15 seconds for exposing the aforesaid black photoresist composition. The exposed glass substrates were developed in a basic developer, and then baked at a temperature of 200° C. for 20 min, to form black rectangular patterns 1 to 10, which had a thickness of 1.5 μm.
  • Each formed black rectangular pattern was measured for its specific radiance of infrared light (with IRE-1 Type 1 Infrared Radiation Measuring Instrument) and chromaticity (Shimadzu UV-2550), and the results were shown in Table 1 below, wherein “□” meant that the comprehensive performance was moderated, and “O” meant the comprehensive performance was good.
  • TABLE 1
    3 4 5 6 7 8 9 10 11 12
    Color mixed Colorant (%) Raven 760 Ultra 14.25 13 11 9 8 7.5 6 6 5 2
    material Infrared B-1 0 2 2 3 2 3 1 0 2 0
    light-emitting B-2 0 0 1 2 3 0 2 0 0 0
    material B-3 0.75 0 0 1 2 1.5 1 3 0 2
    (%)
    Solvent (%) C-1 19.17 19.179 20.974 27.98 26.982 20.982 29.983 18.974 19.23 28.23
    C-2 30 20 20 20 18 30 25 30 35 20
    C-3 10 20 20 12 15 10 5 12 8.75 17.75
    Alkali-soluble resin (%) D-1 10 10 8 7 8 9 10 12 6.25 8.5
    D-2 2 2 4 5 4 4 5 3 8.75 6.5
    Ethenoid unsaturated E-1 10 10 11 11 10 12 12 12 10 5
    monomer (%) E-2 3.8 3.8 2 2 3 2 3 3 5 10
    Photoinitiator (%) F-1 0.007 0.001 0.009 0.006 0.003 0.003 0.008 0.01 0.008 0.01
    F-2 0.008 0.005 0.005 0.004 0.005 0.005 0.004 0.008 0.007 0.005
    Additives (%) G-1 0.002 0.002 0.002 0.002 0.002 0.002 0.001 0.002 0.001 0.001
    G-2 0.013 0.013 0.01 0.008 0.008 0.008 0.004 0.006 0.004 0.004
    Performance Specific Radiance of Infrared Light 0.36 0.53 0.57 0.8 0.83 0.71 0.66 0.6 0.59 0.57
    OD (T = 1.0 um) 4.88 4.8 4.76 4.7 4.65 4.52 4.47 4.46 4.41 2.12
    Comprehensive Effects Δ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ
  • It can be seen from the results as shown in Table 1 that when the ratio of the colorant to the infrared light-emitting material is greater than 6, the specific radiance of infrared light is relatively low, e.g., in Examples 3 and 4. As for Example 12, the content of the color material is relatively low, and thus the colorant content is relatively low, thereby resulting in the low optical density of the black photoresist material (i.e., low OD value).
  • When the content of the infrared light-emitting material in the color mixed material is low, the specific radiance of infrared light of the photoresist composition is also low. Over the increasing of the content of the infrared light-emitting material in the color mixed material, the specific radiance of infrared light of the photoresist composition increases, but does not yet result in remarkable effect on the optical density of the photoresist material.
    • Effect of Infrared Light-Emitting Materials with and Without Surface Modification on the Stability of the Photoresist Comparative Example 1
  • 5 g of a dispersant, BYK 161, was added into 95 g of a solvent, propylene glycol monomethyl ether acetate (PMA), and then 11.1 g of alumina particles were added. The resultant mixture was stirred to be homogeneous, and ground in a sand mill to the extent that the mean particle diameter of alumina is 17 nm, thereby produce an alumina nano-dispersion. The alumina nano-dispersion was subject to removal of solvent, thereby producing alumina nanoparticles.
  • The black pigment RAVEN 760 ULTRA was mixed with the aforesaid alumina nanoparticles at a weight ratio of 19:1 to produce a color mixed material.
  • The comparative black photoresist composition was prepared in accordance with the method of Example 3.
  • The two black photoresist compositions of Example 3 and Comparative Example 1 were placed under shade environment at 0 to 4° C., and then observed for the delamination and precipitation of the photoresist composition.
  • The comparative black photoresist composition: after 24 hours, there were crusting on the surface and some precipitates at the bottom of the containment; and after 48 hours, there appeared a large amount of agglomerates with stirring, and solid particles agglomerated seriously.
  • The black photoresist composition-1: Until 48 hours, there appeared no crusting on the surface or precipitate at the bottom; while stirring did not result in caking or agglomeration.
  • Thus, it can be seen that the black photoresist composition capable of emitting infrared light of the embodiments of the present invention can emit far-infrared light having a health caring effect while maintaining conventional display properties due to the incorporation of surface-modified infrared light-emitting material nanoparticles.

Claims (18)

1. A black photoresist composition capable of emitting infrared light, wherein the black photoresist composition capable of emitting infrared light comprising, based on the total weight of the composition:
2% to 15% of a color mixed material, 30% to 90% of a solvent, 2% to 20% of an alkali-soluble resin, 2% to 20% of an ethenoid unsaturated monomer. 0.01% to 1% of a photoinitiator, and 0.005% to 0.02% of other additives;
wherein, the color mixed material comprises a colorant and surface-modified infrared light-emitting material at a weight ratio of 19:1 to 1:1.
2. The black photoresist composition capable of emitting infrared light of claim 1, wherein the color mixed material comprises the colorant and the surface-modified infrared light-emitting material at a weight ratio of 6:1 to 1:1.
3. The black photoresist composition capable of emitting infrared light of claim 1, wherein the infrared light-emitting material is one or more selected from the group consisting of tourmaline, biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide.
4. The black photoresist composition capable of emitting infrared light of claim 3, wherein the infrared light-emitting material is subject to surface modification with a polymeric material.
5. The black photoresist composition capable of emitting infrared light of claim 4, wherein the polymeric material is a methyl methacrylate-co-styrene-co-maleimide copolymer.
6. The black photoresist composition capable of emitting infrared light of claim 1, wherein the surface-modified infrared light-emitting material has a mean particle diameter of 1 nm to 200 nm.
7. The black photoresist composition capable of emitting infrared light of claim 3, wherein the tourmaline is black tourmaline having a density of 3.06 to 3.26 g/cm3 and a refraction index of 1.62 to 1.64.
8. A method of preparing a black photoresist composition capable of emitting infrared light comprising:
grinding and dispersing an infrared light-emitting material into a solvent to give a nano-dispersion comprising infrared light-emitting material nanoparticles having a mean particle diameter of 1 nm to 200 nm;
modifying the infrared light-emitting material nanoparticles in the nano-dispersion with a polymeric material, followed by removing the solvent, to give polymeric material-modified infrared light-emitting material nanoparticles;
mixing the polymeric material modified infrared light-emitting material nanoparticles with a colorant to give a color mixed material, and
mixing the color mixed material with a solvent, an alkali-soluble resin, an ethenoid an unsaturated monomer, a photoinitiator, and other additives, to give the black photoresist composition capable of emitting infrared light.
9. The method of preparing the black photoresist composition capable of emitting infrared light of claim 8, wherein the infrared light-emitting material is one or more selected from the group consisting of tourmaline, biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide.
10. The method of preparing the black photoresist composition capable of emitting infrared light of claim 8, wherein the polymeric material is a methyl methacrylate-co-styrene-co-maleimide copolymer.
11. A color filter, comprising a Black Matrix formed from the black photoresist composition capable of emitting infrared light of claim 1.
12. A display device comprising the color filter of claim 11.
13. The color filter of claim 11, wherein the color mixed material comprises the colorant and the surface-modified infrared light-emitting material at a weight ratio of 6:1 to 1:1.
14. The color filter of claim 11, wherein the infrared light-emitting material is one or more selected from the group consisting of tourmaline, biological carbon, far-infrared ceramics, bowlder powders, alumina, copper oxide, silver oxide and silicon carbide.
15. The color filter of claim 14, wherein the infrared light-emitting material is subject to surface modification with a polymeric material.
16. The color filter of claim 15, wherein the polymeric material is a methyl methacrylate-co-styrene-co-maleimide copolymer.
17. The color filter of claim 11, wherein the surface-modified infrared light-emitting material has a mean particle diameter of 1 nm to 200 nm.
18. The color filter of claim 14, wherein the tourmaline is black tourmaline having a density of 3.06 to 3.26 g/cm3 and a refraction index of 1.62 to 1.64.
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US10775664B2 (en) * 2017-07-13 2020-09-15 Lg Display Co., Ltd. Display device having bezel pattern and method of manufacturing the same

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